The present invention relates to the use of certain perfume ingredients as an insect repellent, to compositions containing the perfume ingredients and to a method of repelling insects.
Insects have long been known as a nuisance and, for some insect genera, as a health hazard. Mosquitoes, for instance, are a proven vector of diseases, and the genus Aedes in particular is associated with yellow fever, dengue, encephalitis and malaria (Encyclopaedia Britannica). Although the problems may be reduced at source with the use of DDT and other chemical sprays in the breeding areas, fears over the persistence of chlorchemicals combined with increasing mosquito resistance to control chemicals (e.g. insecticides) have led to a reappraisal of the magnitude of the nuisance and the hazard. Physical barriers to the insects are not always possible, e.g. in the open air, where some form of personal repellent is necessary.
It is also a feature of recent times that the more environmentally-aware public tend to question the safety of many chemicals which were formerly taken for granted. One of these is the well-known personal insect repellent N,N-diethyl-m-toluamide (abbreviated as DEET, and commercially available as Delphone(trademark)). This was originally seen as the natural successor to the parent molecule, N,N-diethylbenzamide which was found to be strongly insect repellent but also irritating to human skin (McCabe et al., (1954), J. Org Chem. 19, 493-498). Fears over possible allergenicity, disclosed in European Patent Application EP-A-0 167 266 (Angus Chemical Company), as well as aversion to some of the physical properties of this compound such as oiliness and odour, have led to the search for less hazardous and more aesthetically acceptable methods of repelling insect pests, particularly mosquitoes.
Certain compounds have long been known to possess insect deterrent properties, some of this information coming from what might be termed xe2x80x9cfolk knowledgexe2x80x9d. These materials include widely-known substances such as Citronella, Tolu and Peru Balsams, Eucalyptus oils, Huon Pine and other similar oils [M. Bouvier, International Frag. Co-ord. 29 October 1976]. Other materials known for their deterrent properties include those having camphoraceous odours, such as Camphor itself, Cypress oils, Galbanum etc. [HandR Contact, 36, 1984].
Perfume ingredients with insect repellent properties used either alone, or in a perfume composition, and/or in some form of carrier or base overcome many of the problems highlighted above. Many common types of household insects such as American cockroaches (periplaneta americana) are classified as pests and significant effort has been made to control or eradicate them. A variety of chemicals that are effective in repelling cockroaches has been discovered. These chemicals are used in the household by applying or spraying them to surfaces of walls, floors, cabinets, containers, rugs, upholstery and carpeting, and in potential nesting places for insects, such as inside walls and between floors. They have been used together with hardsurface cleaners (EP-A-0 619 363) and wax floor polishes (U.S. Pat. No. 3,018,217).
It is known in the art that organic materials and essential oils can be repellent against insects. In the art this has been measured in a variety of ways with different insects. The majority of the prior art has been directed towards mosquitoes and in particular the species aedes aegyptii. The results of these studies has led to a list of preferred materials. Surprisingly we have found that additional perfume ingredients, preferably when used above certain limits in perfume compositions can lead to enhanced insect repellency.
PCT Application WO 96/08147 discloses the use of a number of different compounds as insect repellents and also a method by which the repellency of compounds to insects can be reliably tested.
It has now been surprisingly found that a number of perfume ingredients are effective insect repellents.
Accordingly, the present invention provides the use of at least one perfume ingredient selected from the group consisting of
Citral diethyl acetal (Citrathal*),
Tricyclodecenyl allyl ether (also known as 8-(allyloxy)tricyco [5.2.1.0.2.6 ]dec-3-ene) [Fleuroxene*],
2-(2-methylpropyl )-4-hydroxy4-methyltetrahydropyran [Florosa*],
N-methyl-N-phenyl-2-methylbutanamide [Gardamide*],
4-isobutyrate-3-methoxybenzaldehyde [Isobutavan*],
1 -hydroxy-2-methoxy4-propenylbenzene [Isoeugenol*],
2,2,7,7-tetramethyltricyclo[6.2.1.01.6]undecan-5-one [Isolongifolanone*],
7-formyl-5-isopropyl-2-methylbicyclo[2.2.2]oct-2-ene [Maceal*],
3-methyl-5-phenyl-1-pentanal [Mefranal*],
alpha iso methyl ionone (also known as 4-(2,6,6-trimethyl-2-cyclohexen-1 -yl)-3-methyl-3-buten-2-one),
myrcenyl acetate (also known as 2-methyl-6-methylene-7-octen-2-yl acetate) [Neobergamate*],
10-isopropyl-2,7-dimethyloxaspiro [4.5] 3,6-decadiene [Neocaspirene*],
tricyclo[5.2.1.02.6]dec4-en-8-yl 2,2-dimethylpropanoate (Pivacyclene*),
2-phenylethyl pivalate (also known as phenylethyl-2,2-dimethylpropanoate) [Pivarose*]
and 2,4-dimethyl-4-phenyltetrahydrofuran [Rhubafuran*]
as an insect repellent. (*trade marks)
In another aspect, the invention provides a method of repelling insects from an object or an airspace, comprising application to the object or into the airspace, of an effective amount of at least one perfume ingredient selected from the group consisting of the aforementioned perfume ingredients. Typically, the object is a human body or a solid surface such as a wall or floor.
The perfume ingredients from the aforementioned list which are more effective as insect repellents are those which have an octanol-water partition coefficient such that xe2x80x9clog Pxe2x80x9d has a value in the range from 1.0 to 6.0, more preferably 2.0 to 5.0, and particularly 2.5 to 4.5. xe2x80x9clog Pxe2x80x9d is the common logarithm of the octanol-water partition coefficient and is well known in the literature as an indicator of hydrophobicity and water solubility (see Hansch and Leo, Chemical Reviews, 526 to 616 (1971), 71 and Hansch, Quinlan and Lawrence J. Organic Chemistry, 347 to 350 (1968), 33). Where such values are not available in the literature they may be measured directly or approximately estimated using mathematical algorithms. Software providing such estimates is available commercially, for example xe2x80x98LogPxe2x80x99 from Advanced Chemistry Design Inc.
In addition, those perfume ingredients which are more effective as insect repellents have a xe2x80x9cKovatsxe2x80x9d index value in the range from 1150 to 1650, more preferably 1250 to 1600, and particularly 1300 to 1560. Kovats indices are calculated from the retention time in a gas chromatographic measurement referenced to the retention time for alkanes (see Kovats, Helv. Chim. Acta 41, 1915 (1958)). Indices based on the use of a non-polar stationary phase have been used in the perfumery industry for some years as a descriptor relating to the molecular size and boiling point of ingredients. A review of Kovats indices in the perfume industry is given by T Shibamoto in xe2x80x9cCapillary Gas Chromatography in Essential Oil Analysisxe2x80x9d, P Sandra and C Bicchi (editors), Huethig (1987), pages 259 to 274. A common non-polar phase which is suitable is 100% dimethyl polysiloxane, as supplied, for example, under a variety of trade names such as HP-1 (Hewlett Packard), CP Sil 5 CB (Chrompak), OV-1 (Ohio Valley) and Rtx-1 (Restek).
A further property of the aforementioned perfume ingredients which confers good performance as an insect repellent is a capability of forming hydrogen bonds of greater than 60 on the Koppel Pal""m scale (J. Chem. Soc. Perkin Trans. 2, 1976, pp 1628).
The insect repellent perfume ingredients described herein are preferably used in a composition, more preferably in a perfume composition, preferably at a concentration of at least 10%, more preferably at least 30%, and particularly at least 50% by weight. The composition used in the invention comprises at least one, and, more preferably, 3 or 4 of the perfume ingredients described herein. The individual perfume ingredients are preferably present at a concentration in the range from 0.1% to 40%, more preferably, 0.5% to 20% by weight. The perfume composition may contain other known insect repellents, preferably of previously known insect repellent perfume ingredients, preferably at a concentration of at least 10%, more preferably at least 30%, and particularly at least 50% by weight.
Compositions containing more than one of the aforementioned insect repellent perfume ingredients preferably contain at least one such perfume ingredient having a xe2x80x9clog Pxe2x80x9d value in the range 1.0 to 6.0 or at least one such perfume ingredient having a Kovats index in the range 1150 to 1650, as hereinbefore defined, or at least one such perfume ingredient capable of forming hydrogen bonds of greater than 60 on the Koppel Pal""m scale.
Preferably, the perfume ingredients described herein are used to repel insects, such as mosquitoes, particularly members of the genus Aedes and cockroaches.
Compositions used in accordance with the invention preferably constitute, or comprise, personal products or cosmetics for use on the skin and/or hair. Examples of such products include fine fragrances, colognes, skin creams, skin lotions, deodorants, talcs, bath oils, soaps, shampoos, hair conditioners and styling agents.
Alternatively, compositions used in accordance with the invention may constitute, or be comprised in, household products such as: air fresheners (including xe2x80x9cheatedxe2x80x9d air fresheners in which insect repellent substances are released upon heating, e.g. electrically, or by burning [e.g. joss-sticks, candles]); hard surface cleaners; or laundry products (e.g. laundry detergent-containing compositions, conditioners).
Preferably the cosmetics, personal products and household products defined above comprise between 0.1% and 20%, more preferably 0.2% to 10% by weight of a composition used in accordance with the invention.
The compositions used in the invention may comprise additional materials to produce desired products such as pleasing perfumes with useful repellent activity. Other materials which may be present in the compositions (at concentrations from 0 to 99.95% w/w) include fragrances, solvents, diluents and fixatives known in the art, such as:
Aldehyde C11 (Undecylenic Aldehyde); Aldehyde iso C11 (GIV); Allspice oil; Allyl cyclohexyl propionate; Amyl salicylate; Amylcinnamic aldehyde; Anethole; Anisic alcohol; Anisic aldehyde; Applinal (Q); Bay oil; Benzyl acetate; Benzyl benzoate; Benzyl cinnamate; Benzyl propionate; Benzyl salicylate; Bourgeonal (Q); Brahmanol; Camphor powder synthetic; Cedarwood Virginian; Cedrenol; Cedryl acetate; Celestolide (IFF); Cineole; Cinnamic alcohol; cinnamic aldehyde; Cinnamon Leaf Oil: Cinnamyl acetate; cis-3-Hexenol; Citral; Citronella oil; Citronellal; Citronellol; Citronellyl acetate; Citronellyl oxyacetaldehyde; Clove oil; Coriander oil; Coumarin; Cuminic aldehyde; Cyclamen aldehyde; Decanal; 9-Decenol; Dibenzyl ether; Dibutyl phthalate; Diethyl Phthalate; Dihydromyrcenol; Dimethyl anthranilate; Dimethyl phthalate; Dimycretol (IFF); diphenylmethane; Diphenyl oxide; Dimethyl benzyl carbinyl acetate; Dodecanol; Dodecanal; Elemi oil; Ethyl methyl phenyl glycidate; Ethyl cinnamate; Ethyl safranate (Q); ethyl vanillin; Eugenol; Evergreen oils (Pine oils etc.); gamma-Nonalactone; gamma-undecalactone; Geraniol; Geranium bourbon; Geranyl acetate; Geranyl formate; Gum Benzoin; Heliotropin; Hercolyn D (HER); Hexyl benzoate; Hexylcinnamic aldehyde; Hydratropic aldehyde dimethyl acetal; Hydroxycitronellal; Hydroxycitronellal dimethyl acetal; Indole; iso Bomyl acetate; Isopropyl myristate; Iso-cyclocitral (GIV, IFF); Jasmacyclene; Jasmin oil; Lavandin Abrialis; Lavender oil; Lilial (GIV); Linalol; Linalyl acetate; Menthol Laevo; Methyl anthranilate; Methyl cedryl ketone; Methyl dihydrojasmonate; Methyl ionone; Methyl myristate; Methyl naphthyl ketone; Methyl salicylate; Moss treemoss; Musk ketone; Nerol; Nerolin Bromelia; Neryl acetate; Nonanal; Oakmoss absolute; Octanol Olibanum resionoid; para-Cresyl phenylacetate; para-Methoxyacet6phenone; Patchouli oil; Peppermint oil; Petitgrain oil; 2-Phenoxyethanol; Phenoxyethyl iso butyrate; Phenylethylacetate; Phenyethyl alcohol; Phenylethyl butyrate; Phenylethyl phenylacetate; Pimento oil; Pinene, alpha; Para-tert. butyl-cyclohexyl acetate; Resinoid Benzoin Siam; Rose oil; Rosemary oil; Sandalwood oil; terpineol; Tetrahydrolinalol; Tetrahydromuguol (IFF); Thyme Red; Undecanal; Vanillin; Verbena oil; Vetyvert Bourbon; Yara and Ylang ylang.
Compounds are obtainable from the suppliers as indicated below: for those compounds labelled xe2x80x9c(Q)xe2x80x9d,xe2x80x94Quest International, xe2x80x9c(IFF)xe2x80x9dxe2x80x94International Flavours and Fragrances, Inc., xe2x80x9c(GIV)xe2x80x9dxe2x80x94Givaudan, xe2x80x9c(HER)xe2x80x9dxe2x80x94Hercules B.V.
Other active and non-active materials may be present, such as:
acidic mucopolysaccharides and their salts, Aesculus hipocastanum, aloe barbadenisis Mil (Aloe Vera Linne), xcex1-hydroxycarboxylic acids, xcex1-ketocarboxylic acids, amide derivatives, amino acids, amphiphilic cyclodextrin derivatives, xcex2-sitosterol, carboxy vinyl polymer water soluble salts, carboxymethyl cellulose, carrageenan, chitin, chitosan, cholesterol, cholesterol fatty acid ester, collagen, dicarboxylic acid monostearyl esters, di-fatty acid glycerol esters, digalactosyl diglyceride, ersterol, ethanol, extract of Swertia japonica Makino, fatty acids, fatty acid citrate esters, fatty alcohols, ginseng extract, glucose esters of higher fatty acids, guar gum, gum arabic, Hamamelidaceae (Hamamelis Virginiana Witch hazel), hyaluronic acid, hydrochyloesterol, hydroxybenzoic acids, isomaltose, isopropyl alcohol, lactose, lanosterol, lipids extracted from the biomass of microorganisms, yeasts, moulds and bacteria, liposomes, locust bean gum, low molecular acidic mucopolysaccharides and their salts, low molecular weight humectant components, maltose, mineral oils, mineral powders, mono cis alkenoic acid, mucopolysaccharides, mycosterol, N-acyl lysines, N-isostearyl lysine, N-lauroyl lysine, N-myristyl lysine, N-palmitoyl lysine, N-stearoyl lysine, natrium type bentonite, natural or synthetic aminoacid with protein or peptide bonds, NMF ingredients, nonvolatile silicones, oil agents, oil matter, oligosaccharides, organic acids, pantothenic acid and its derivatives, petroleum jelly, phosphatidyl ethanolamine, phosphatidylcholine, phospholipids, polysaccharides, polyvinyl alcohol, polypeptides, proteins, raffinose, saponins, sodium hyaluronate, sources of linoleic acid, sterols, sterol esters, stigmasterol, sucrose, sugar esters of higher fatty acids, sulphatide, sunscreens, surfactants, talc, thymosterol, tocopherol, mono-, di- or tri-glycerides, vitamins and analogues, vitamin E and/or its ester compounds, volatile silicone fluids, water-soluble moisture-retaining agents, water-soluble polymers and waxes.
The perfume ingredients used in the present invention can be used as the sole insect repellent in a composition or may be used in combination with other compounds which are effective insect repellents, including previously known insect repellent perfume ingredients.
Thus, a further aspect of the invention comprises a mixture the perfume ingredients described herein with a known insect repellent. Known insect repellents which are suitable for use in a mixture with at least one perfume ingredient used in the present invention include N,N-diethyl-m-toluamide (DEET); N,N-diethylbenzamide; citronella; Tolu balsam; Peru balsam; Eucalyptus oil; Huon pine oil; camphor; cypress oil; galbanum; diethyl phthalate; dimethyl phthalate; dibutyl phthalate; 1,2,3a,4,5a,6,7,8,9,9a,9b-dodecahydro-3a,6,6,9a-tetramethyinaphtho[2,1 -b] furan; 4-(tricyclo[5.2.1.02.6]decylidene-8)butanal; 1-ethoxy-1-(2xe2x80x2-phenylethoxy)ethane; acetyl cedrene an propylidene phthalide.
A further composition according to the invention comprises a mixture of at least one of the aforementioned perfume ingredients and a further compound, said further compound being present in an amount which is sufficient to ensure that said further compound contributes to said composition an insect repellent effect equivalent to a repellency of at least 10% as determined by the insect repellency test defined in Example 1. Preferably, the further compound is present in said composition in an amount which is sufficient to ensure that said further compound contributes an insect repellent effect equivalent to a repellency of at least 20% as determined by said insect repellency test. More preferably, the insect repellent effect contributed by the further compound is equivalent to a repellency of at least 30%.